JPWO2015080103A1 - Purging agent and purging method using the same - Google Patents
Purging agent and purging method using the same Download PDFInfo
- Publication number
- JPWO2015080103A1 JPWO2015080103A1 JP2015550937A JP2015550937A JPWO2015080103A1 JP WO2015080103 A1 JPWO2015080103 A1 JP WO2015080103A1 JP 2015550937 A JP2015550937 A JP 2015550937A JP 2015550937 A JP2015550937 A JP 2015550937A JP WO2015080103 A1 JPWO2015080103 A1 JP WO2015080103A1
- Authority
- JP
- Japan
- Prior art keywords
- resin
- purging
- shear viscosity
- temperature
- purging agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- ITMIAZBRRZANGB-UHFFFAOYSA-N but-3-ene-1,2-diol Chemical compound OCC(O)C=C ITMIAZBRRZANGB-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- ZQPPMHVWECSIRJ-MDZDMXLPSA-M elaidate Chemical class CCCCCCCC\C=C\CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-MDZDMXLPSA-M 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IEZWOVIWXFLQTP-UHFFFAOYSA-N hydroperoxyethene Chemical class OOC=C IEZWOVIWXFLQTP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-M linolenate Chemical class CC\C=C/C\C=C/C\C=C/CCCCCCCC([O-])=O DTOSIQBPPRVQHS-PDBXOOCHSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940105132 myristate Drugs 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- PBSASXNAZJHOBR-UHFFFAOYSA-N n-(2-methylpropyl)prop-2-enamide Chemical compound CC(C)CNC(=O)C=C PBSASXNAZJHOBR-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 229940039748 oxalate Drugs 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical class CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/27—Cleaning; Purging; Avoiding contamination
- B29C48/2715—Cleaning; Purging; Avoiding contamination of plasticising units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/086—EVOH, i.e. ethylene vinyl alcohol copolymer
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Detergent Compositions (AREA)
Abstract
本発明のパージング剤はエチレン−ビニルエステル系共重合体ケン化物樹脂を含む被パージ樹脂のパージに用いられ、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩を、比較的多量に含有する炭化水素系樹脂組成物であり、下記式より求められるせん断粘度比が特定範囲を満たす。せん断粘度比 = η(X)/η(Y)[ここで、η(X)は温度230℃、せん断速度12.2sec−1のせん断粘度(Pa・S)であり、η(Y)は温度230℃、せん断速度1824sec−1のせん断粘度(Pa・S)である。]The purging agent of the present invention is used for purging a resin to be purged containing an ethylene-vinyl ester copolymer saponified resin, and contains at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts. The hydrocarbon-based resin composition is contained in a relatively large amount, and the shear viscosity ratio obtained from the following formula satisfies a specific range. Shear viscosity ratio = η (X) / η (Y) [where η (X) is a shear viscosity (Pa · S) at a temperature of 230 ° C. and a shear rate of 12.2 sec−1, and η (Y) is a temperature. The shear viscosity (Pa · S) is 230 ° C. and the shear rate is 1824 sec−1. ]
Description
本発明は、熱可塑性樹脂を溶融成形する装置に用いるパージング剤に関するものであり、特に、エチレン−ビニルエステル系共重合体ケン化物樹脂に対して好適なパージング剤およびこれを用いたパージング方法に関するものである。 The present invention relates to a purging agent used in an apparatus for melt-molding a thermoplastic resin, and more particularly to a purging agent suitable for an ethylene-vinyl ester copolymer saponified resin and a purging method using the same. It is.
従来、エチレン−ビニルエステル系共重合体ケン化物樹脂(以下、EVOH樹脂と称することがある)、ポリビニルアルコール系樹脂(以下、PVA樹脂と称することがある)、ポリアミド系樹脂(以下、PA樹脂と称することがある)等の極性の高い熱可塑性樹脂は、ガスバリア性に優れており、一般的に溶融成形法によって食品等の包装用フィルムや容器などに成形して使用されている。 Conventionally, ethylene-vinyl ester copolymer saponified resin (hereinafter sometimes referred to as EVOH resin), polyvinyl alcohol resin (hereinafter sometimes referred to as PVA resin), polyamide resin (hereinafter referred to as PA resin). High-polarity thermoplastic resins, such as sometimes referred to, are excellent in gas barrier properties, and are generally used by being molded into packaging films or containers for foods, etc. by a melt molding method.
しかしながら、上記熱可塑性樹脂を長時間にわたって溶融成形する場合、該熱可塑性樹脂の一部が押出機等の溶融成形機の樹脂流路内に長時間滞留し、ゲル化,熱劣化,分解などが生じて製品中にスジが発生したり、ゲルが製品に混入して製品不良を生じたりするという問題があった。 However, when the thermoplastic resin is melt-molded for a long time, a part of the thermoplastic resin stays in the resin flow path of a melt-molding machine such as an extruder for a long time, causing gelation, thermal deterioration, decomposition, etc. As a result, there are problems that streaks are generated in the product, and gel is mixed into the product to cause a product defect.
このように、製品にスジ発生やゲルの混入が見られた場合には、製造作業を止め、パージング剤を用いて溶融成形機の樹脂流路内に存在し、こびり付いたりしている熱可塑性樹脂を洗浄・除去することが有効である。 In this way, when streaks are generated or gel is mixed in the product, the manufacturing operation is stopped, and the thermoplastic resin that is stuck in the resin flow path of the melt molding machine using a purging agent is stuck. It is effective to wash and remove.
従来、かかるパージング剤として、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩を比較的多量に含有する炭化水素系樹脂組成物を用いたパージング剤が知られている(例えば、特許文献1参照)。
このパージング剤は、被パージ樹脂に金属塩が移行し、被パージ樹脂を分解する作用を有することで、優れた洗浄効果が得られるというものである。Conventionally, as such a purging agent, a purging agent using a hydrocarbon-based resin composition containing a relatively large amount of at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts is known. (For example, refer to Patent Document 1).
This purging agent has an action of transferring a metal salt to the purged resin and decomposing the purged resin, thereby obtaining an excellent cleaning effect.
しかしながら、特許文献1のパージング剤では、溶融成形機のダイ部分のような、流路が狭く高温の苛酷な環境の箇所において、洗浄効果が不充分であることが判明した。 However, the purging agent of Patent Document 1 has been found to have an insufficient cleaning effect in a severe environment with a narrow flow path and high temperature, such as a die portion of a melt molding machine.
したがって、本発明は、より洗浄効果の優れるパージング剤の提供を目的とするものである。 Accordingly, an object of the present invention is to provide a purging agent having a more excellent cleaning effect.
本発明者は上記実情に鑑み鋭意検討した結果、炭化水素系樹脂と、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩とを含み、該炭化水素系樹脂に対する該金属塩の含有量が金属に換算して1重量%を超えて20重量%以下であり、下記式より求められるせん断粘度比が12〜16であるパージング剤が、特にエチレン−ビニルエステル系共重合体ケン化物樹脂を含む被パージ樹脂のパージに効果的であることに着目した。
せん断粘度比 = η(X)/η(Y)
[ここで、η(X)は温度230℃、せん断速度12.2sec−1のせん断粘度(Pa・S)であり、η(Y)は温度230℃、せん断速度1824sec−1のせん断粘度(Pa・S)である。]As a result of intensive studies in view of the above circumstances, the present inventor includes a hydrocarbon resin and at least one metal salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt. A purging agent in which the content of the metal salt is more than 1% by weight and not more than 20% by weight in terms of metal and the shear viscosity ratio obtained from the following formula is 12 to 16, particularly ethylene-vinyl ester-based co-agents. It has been noted that it is effective for purging a purged resin containing a polymer saponified resin.
Shear viscosity ratio = η (X) / η (Y)
[Here, eta (X) is a temperature 230 ° C., a shear viscosity of the shear rate 12.2sec -1 (Pa · S), η (Y) is a temperature 230 ° C., the shear viscosity of the shear rate 1824sec -1 (Pa -S). ]
すなわち、本発明は、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩を比較的多量に含有する炭化水素系樹脂組成物をパージング剤として用いる場合において、特定の高せん断速度と低せん断速度のせん断粘度比が大きいパージング剤を用いることを特徴とするものである。 That is, the present invention uses a hydrocarbon resin composition containing a relatively large amount of at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts as a purging agent. A purging agent having a large shear viscosity ratio between a high shear rate and a low shear rate is used.
なお、押出機等の溶融成形機を用いて熱可塑性樹脂(被パージ樹脂)を溶融成形するにあたり、樹脂流路内で滞留が生じる箇所においては、一般に低せん断速度のせん断粘度が高いほど、滞留した該熱可塑性樹脂を洗浄し、除去するパージ性能が良好であると考えられる。 When melt-molding a thermoplastic resin (resin to be purged) using a melt-molding machine such as an extruder, generally, the higher the shear viscosity at a low shear rate, the longer the residence in the resin flow path. It is considered that the purge performance for washing and removing the thermoplastic resin is good.
しかしながら、意外にも、特定のせん断速度によるせん断粘度比が大きいものを用いることにより、溶融成形機のダイ部分のように、流路が狭く高温の苛酷な環境の箇所においても優れた洗浄効果が得られることを見出し、本発明を完成した。 However, surprisingly, by using a material having a large shear viscosity ratio due to a specific shear rate, an excellent cleaning effect can be obtained even in a severe environment where the flow path is narrow and the temperature is narrow like the die part of a melt molding machine. As a result, the present invention was completed.
本発明のパージング剤は、230℃、荷重2160gにおけるメルトフローレートが、0.2〜20g/10分であることが好ましい。 The purging agent of the present invention preferably has a melt flow rate of 0.2 to 20 g / 10 min at 230 ° C. and a load of 2160 g.
また、本発明は、上記パージング剤を用いる、溶融成形機内に存在する被パージ樹脂のパージング方法に関する。 The present invention also relates to a method for purging a purged resin existing in a melt molding machine using the above-described purging agent.
また、本発明は、上記パージング剤を充填すること、溶融成形機内部をパージング剤で満たした状態でスクリューを停止し、5分〜5時間放置すること、およびパージング剤を排出することを含む、溶融成形機内に存在する被パージ樹脂のパージング方法に関する。 Further, the present invention includes filling the above-mentioned purging agent, stopping the screw in a state where the melt molding machine is filled with the purging agent, and leaving it for 5 minutes to 5 hours, and discharging the purging agent. The present invention relates to a purging method for a resin to be purged existing in a melt molding machine.
本発明においては、アルカリ金属塩およびアルカリ土類金属塩の金属塩のうち少なくとも1種を比較的多量に含有する炭化水素系樹脂組成物をパージング剤として用いる場合において、かかるパージング剤が、特定範囲のせん断粘度比を満たすことにより、溶融成形機内の被パージ樹脂、特にエチレン−ビニルエステル系共重合体ケン化物樹脂を含む被パージ樹脂の洗浄・除去効果に優れ、溶融成形機のダイ部分のように、流路が狭く高温の苛酷な環境においても優れた洗浄効果が発揮されるものである。 In the present invention, when a hydrocarbon-based resin composition containing a relatively large amount of at least one of alkali metal salts and alkaline earth metal salts is used as a purging agent, the purging agent has a specific range. By satisfying the shear viscosity ratio, the resin to be purged in the melt molding machine, particularly the purged resin including the saponified resin of ethylene-vinyl ester copolymer, is excellent in cleaning and removing effect, like the die part of the melt molding machine. In addition, an excellent cleaning effect is exhibited even in a severe environment with a narrow flow path and a high temperature.
以下、本発明の構成につき詳細に説明するが、これらは望ましい実施態様の一例を示すものであり、これらの内容に特定されるものではない。 Hereinafter, although it demonstrates in detail about the structure of this invention, these show an example of a desirable embodiment and are not specified by these content.
本発明のパージング剤は、押出機等の溶融成形機を用いて熱可塑性樹脂(被パージ樹脂)を溶融成形するにあたり、溶融成形機中の樹脂流路内に滞留した該熱可塑性樹脂を洗浄し、除去するために用いるものである。 The purging agent of the present invention cleans the thermoplastic resin staying in the resin flow path in the melt molding machine when melt molding the thermoplastic resin (resin to be purged) using a melt molding machine such as an extruder. Used for removal.
本発明における押出機のバレル温度とは、押出機のバレルの表面温度を意味する。押出機のバレルが複数のセクションを有しており、個々のセクションが異なる温度に設定されている場合は、そのうちの最高温度をバレル温度とする。 In the present invention, the barrel temperature of the extruder means the surface temperature of the barrel of the extruder. When the barrel of the extruder has a plurality of sections and each section is set to a different temperature, the highest temperature is set as the barrel temperature.
<パージング剤>
本発明のパージング剤は炭化水素系樹脂をベースとし、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩を比較的多量に含有する組成物である。
本発明のパージング剤組成物に対する炭化水素系樹脂の含有量は、通常80重量%以上であり、好ましくは85重量%以上である。<Purging agent>
The purging agent of the present invention is a composition containing a relatively large amount of at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts based on a hydrocarbon resin.
The content of the hydrocarbon resin in the purging agent composition of the present invention is usually 80% by weight or more, preferably 85% by weight or more.
[炭化水素系樹脂]
本発明のパージング剤のベースとなる炭化水素系樹脂とは、炭化水素系モノマーを通常80モル%以上の主モノマーとする、分子量が通常1万以上の高分子であり、主鎖が炭素結合のみで構成されるポリマーである。
かかる炭化水素系樹脂は、樹脂の極性が低い為、溶融成形機を構成する金属に付着しにくいという性質を有する。
パージング剤の排出性の点から、炭化水素系モノマー以外の共重合可能なモノマーの含有量は、20モル%未満であることが好ましい。[Hydrocarbon resin]
The hydrocarbon resin used as the base of the purging agent of the present invention is a polymer having a hydrocarbon monomer as a main monomer of usually 80 mol% or more and a molecular weight of usually 10,000 or more, and the main chain is composed of only carbon bonds. It is a polymer composed of
Such a hydrocarbon resin has a property that it is difficult to adhere to the metal constituting the melt molding machine because the polarity of the resin is low.
From the viewpoint of discharging properties of the purging agent, the content of the copolymerizable monomer other than the hydrocarbon-based monomer is preferably less than 20 mol%.
上記炭化水素系樹脂とは例えば、脂肪族炭化水素系モノマーを主体としたポリオレフィン系樹脂、芳香族炭化水素系モノマーを主体としたポリスチレン系樹脂が挙げられる。 Examples of the hydrocarbon resin include polyolefin resins mainly composed of aliphatic hydrocarbon monomers and polystyrene resins mainly composed of aromatic hydrocarbon monomers.
脂肪族炭化水素系モノマーを主体としたポリオレフィン系樹脂について説明する。脂肪族炭化水素系モノマーとして具体的にはエチレン、プロピレン、ブテン等が挙げられる。
ポリオレフィン系樹脂は、これらの脂肪族炭化水素系モノマーからなるホモポリマー、2種以上のオレフィンモノマーのランダムコポリマー、ブロックコポリマーをいう。
例えば、超低密度ポリエチレン、(直鎖状)低密度ポリエチレン、高密度ポリエチレン、エチレン−プロピレン共重合体、エチレン−オクテン共重合体、エチレン−ヘキセン共重合体等のエチレン−αオレフィン共重合体、等のポリエチレン系樹脂;ポリプロピレン、プロピレン−エチレン共重合体、プロピレン−ブテン共重合体等のプロピレン−αオレフィン共重合体、等のポリプロピレン系樹脂;ポリブテン、ポリメチルペンテン等が挙げられる。The polyolefin resin mainly composed of aliphatic hydrocarbon monomers will be described. Specific examples of the aliphatic hydrocarbon monomer include ethylene, propylene, and butene.
The polyolefin resin refers to a homopolymer composed of these aliphatic hydrocarbon monomers, a random copolymer of two or more olefin monomers, and a block copolymer.
For example, ultra-low density polyethylene, (linear) low density polyethylene, high density polyethylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-α olefin copolymer such as ethylene-hexene copolymer, Polypropylene resins such as polyethylene resins such as polypropylene, propylene-ethylene copolymers, propylene-α olefin copolymers such as propylene-butene copolymers; polybutenes, polymethylpentenes and the like.
芳香族炭化水素系モノマーを主体としたポリスチレン系樹脂について説明する。芳香族炭化水素系モノマーとして具体的にはスチレン、メチルスチレン等が挙げられる。これらの芳香族炭化水素系モノマーからなるホモポリマー、2種以上のモノマーのランダムコポリマー、ブロックコポリマーが、ポリスチレン系樹脂として挙げられる。 A polystyrene resin mainly composed of an aromatic hydrocarbon monomer will be described. Specific examples of the aromatic hydrocarbon monomer include styrene and methylstyrene. Examples of the polystyrene resin include homopolymers composed of these aromatic hydrocarbon monomers, random copolymers of two or more monomers, and block copolymers.
パージング剤の排出性と経済性の点から、炭化水素系樹脂として好ましくはポリエチレン系樹脂またはポリプロピレン系樹脂であり、特に好ましくはポリエチレン系樹脂であり、殊に好ましくは低密度ポリエチレン、さらには直鎖状低密度ポリエチレンである。 From the viewpoint of the dischargeability and economic efficiency of the purging agent, the hydrocarbon resin is preferably a polyethylene resin or a polypropylene resin, particularly preferably a polyethylene resin, particularly preferably a low density polyethylene, and even a linear resin. Low density polyethylene.
本発明においては、特定のせん断速度(sec−1)によるせん断粘度比が大きいパージング剤を用いるのが特徴であるが、パージング剤のベースとなる炭化水素系樹脂において、特定のせん断速度(sec−1)でのせん断粘度比をコントロールすることが好ましい。In the present invention, a purging agent having a large shear viscosity ratio at a specific shear rate (sec −1 ) is used. However, in the hydrocarbon resin used as the base of the purging agent, a specific shear rate (sec − It is preferable to control the shear viscosity ratio in 1 ).
温度230℃、せん断速度12.2sec−1の上記炭化水素系樹脂のせん断粘度:η(x)は、通常1500〜4500Pa・Sであり、好ましくは2000〜4000Pa・Sであり、特に好ましくは2500〜3500Pa・Sである。The shear viscosity: η (x) of the above hydrocarbon-based resin at a temperature of 230 ° C. and a shear rate of 12.2 sec −1 is usually 1500 to 4500 Pa · S, preferably 2000 to 4000 Pa · S, particularly preferably 2500. ˜3500 Pa · S.
温度230℃、せん断速度1824sec−1の上記炭化水素系樹脂のせん断粘度:η(y)は、通常80〜350Pa・Sであり、好ましくは120〜300Pa・Sであり、特に好ましくは160〜250Pa・Sである。The above-mentioned hydrocarbon resin having a temperature of 230 ° C. and a shear rate of 1824 sec −1 has a shear viscosity η (y) of usually 80 to 350 Pa · S, preferably 120 to 300 Pa · S, particularly preferably 160 to 250 Pa. -S.
かかる炭化水素系樹脂のせん断粘度比は、下記式より求められるものであり、通常13.0〜17.0であり、好ましくは13.5〜16.5であり、特に好ましくは14.0〜15.5Pa・Sである。
せん断粘度比 = η(x)/η(y)
[ここで、η(x)は温度230℃、せん断速度12.2sec−1のせん断粘度(Pa・S)であり、η(y)は温度230℃、せん断速度1824sec−1のせん断粘度(Pa・S)である。]
なお、上記の炭化水素系樹脂のせん断粘度比は、キャピラリーレオメーター(流動特性測定装置)を用いて230℃・各せん断速度のせん断粘度を測定し、その結果から算出することができる。The shear viscosity ratio of such a hydrocarbon-based resin is obtained from the following formula, and is usually 13.0 to 17.0, preferably 13.5 to 16.5, and particularly preferably 14.0 to 14.0. 15.5 Pa · S.
Shear viscosity ratio = η (x) / η (y)
[Here, η (x) is the temperature 230 ° C., a shear viscosity of the shear rate 12.2sec -1 (Pa · S), η (y) is a temperature 230 ° C., the shear viscosity of the shear rate 1824sec -1 (Pa -S). ]
The shear viscosity ratio of the hydrocarbon resin can be calculated from the results obtained by measuring the shear viscosity at 230 ° C. and each shear rate using a capillary rheometer (flow characteristic measuring device).
また、上記炭化水素系樹脂の密度は、JIS K7112(1999)の規定に従って測定した値で、通常0.85〜0.98g/cm3であり、さらには0.90〜0.95g/cm3であり、好ましくは0.91〜0.94g/cm3であり、より好ましくは0.92〜0.93g/cm3である。かかる値が上記範囲である場合、パージング効果がより顕著に得られる傾向がある。The density of the hydrocarbon resin is a value measured in accordance with the provisions of JIS K7112 (1999), is usually 0.85~0.98g / cm 3, more 0.90~0.95g / cm 3 Preferably 0.91 to 0.94 g / cm 3 , more preferably 0.92 to 0.93 g / cm 3 . When this value is in the above range, the purging effect tends to be obtained more remarkably.
また、上記炭化水素系樹脂のメルトフローレート(MFR)は、190℃、荷重2160g条件下で、通常0.1〜50g/10分であり、好ましくは0.2〜10g/10分であり、より好ましくは0.5〜5g/10分である。かかる値が上記範囲である場合、パージング効果がより顕著に得られる傾向がある。 Further, the melt flow rate (MFR) of the hydrocarbon-based resin is usually 0.1 to 50 g / 10 minutes, preferably 0.2 to 10 g / 10 minutes under a condition of 190 ° C. and a load of 2160 g, More preferably, it is 0.5-5 g / 10min. When this value is in the above range, the purging effect tends to be obtained more remarkably.
上記炭化水素系樹脂の数平均分子量は、GPC(ゲル透過クロマトグラフ)にてポリスチレンを標準として測定した値で通常1×104〜5×104であり、好ましくは2×104〜4×104であり、より好ましくは3×104〜3.8×104であり、特に好ましくは3×104〜3.5×104である。かかる値が上記範囲である場合、パージング効果がより顕著に得られる傾向がある。The number average molecular weight of the hydrocarbon-based resin is usually 1 × 10 4 to 5 × 10 4 , and preferably 2 × 10 4 to 4 × as measured by GPC (gel permeation chromatography) with polystyrene as a standard. 10 is 4, more preferably 3 × 10 4 to 3.8 × 10 4, particularly preferably 3 × 10 4 to 3.5 × 10 4. When this value is in the above range, the purging effect tends to be obtained more remarkably.
上記炭化水素系樹脂の分子量の分散度(重量平均分子量/数平均分子量)は、通常3〜6であり、好ましくは3.2〜5であり、特に好ましくは3.5〜4.5である。かかる値が上記範囲である場合、パージング効果がより顕著に得られる傾向がある。 The molecular weight dispersity (weight average molecular weight / number average molecular weight) of the hydrocarbon resin is usually 3 to 6, preferably 3.2 to 5, particularly preferably 3.5 to 4.5. . When this value is in the above range, the purging effect tends to be obtained more remarkably.
[金属塩]
本願発明のパージング剤は炭化水素系樹脂をベースとし、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩を、比較的多量に含有する組成物である。
従って、本願発明のパージング剤の炭化水素系樹脂に対する該金属塩の含有量は、金属に換算した値にて1重量%を超えて20重量%以下であり、特に好ましくは1.2〜10重量%であり、殊に好ましくは1.5〜3重量%である。かかる量が多すぎる場合、生産性や経済性が低下する傾向があり、少なすぎる場合、洗浄効果が不十分になるという傾向がある。[Metal salt]
The purging agent of the present invention is a composition based on a hydrocarbon resin and containing a relatively large amount of at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts.
Accordingly, the content of the metal salt with respect to the hydrocarbon resin of the purging agent of the present invention is more than 1 wt% and not more than 20 wt%, particularly preferably 1.2 to 10 wt% in terms of metal. %, Particularly preferably 1.5 to 3% by weight. If the amount is too large, the productivity and economy tend to decrease, and if it is too small, the cleaning effect tends to be insufficient.
上記アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩におけるアルカリ金属およびアルカリ土類金属とは、被パージ樹脂を分解する機能を有するものである。具体的に、アルカリ金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウムが挙げられ、アルカリ土類金属としては、べリリウム、マグネシウム、カルシウム、ストロンチウム、バリウムが挙げられる。中でも易入手性、経済性、パージング性能の点で、アルカリ土類金属が好ましく、特に好ましくはマグネシウム、カルシウムである。 The alkali metal and alkaline earth metal in at least one metal salt selected from the group consisting of the alkali metal salts and alkaline earth metal salts have a function of decomposing the purged resin. Specifically, examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium. Among these, alkaline earth metals are preferred, and magnesium and calcium are particularly preferred from the viewpoints of easy availability, economy, and purging performance.
上記アルカリ金属塩およびアルカリ土類金属塩の金属塩は、有機塩や無機塩が挙げられる。かかる塩は、樹脂組成物中の分散性の点から、低分子化合物であることが好ましい。 Examples of the metal salts of the alkali metal salt and alkaline earth metal salt include organic salts and inorganic salts. Such a salt is preferably a low molecular compound from the viewpoint of dispersibility in the resin composition.
上記有機塩とはカルボン酸塩を意味し、例えば、酢酸塩、シュウ酸塩、ラウリン酸塩、ミリスチン酸塩、パルミチン酸塩、ステアリン酸塩、アラギン酸塩、ヘプタデシル酸塩、ベヘン酸塩、オレイン酸塩、エライジン酸塩、エリカ酸塩、リノール酸塩、リノレイン酸塩、リシノール酸塩、ヒドロキシステアリン酸塩、モンタン酸塩、イソステアリン酸塩、エポキシステアリン酸等が挙げられる。
中でも、界面活性能を有する点で、炭素数が比較的多い長鎖脂肪族カルボン酸塩が好ましい。好ましくは炭素数10〜25のカルボン酸塩であり、より好ましくは炭素数12〜22のカルボン酸塩であり、特に好ましくは炭素数14〜20のカルボン酸塩である。炭素数が多すぎる場合、汎用性に欠ける傾向があり、炭素数が少なすぎる場合、溶融時の界面活性不足によってパージング性能が不足する傾向がある。
すなわち、有機塩として好ましくは炭素数14〜20のカルボン酸の第2族金属塩であり、最も好ましくは炭素数14〜20のカルボン酸マグネシウム塩である。The organic salt means a carboxylate, such as acetate, oxalate, laurate, myristate, palmitate, stearate, alginate, heptadecylate, behenate, olein Acid salts, elaidate salts, elicitate salts, linoleate salts, linolenate salts, ricinoleate salts, hydroxy stearates, montanates, isostearates, epoxy stearates and the like.
Among these, a long-chain aliphatic carboxylate having a relatively large number of carbon atoms is preferable from the viewpoint of having surface activity. Preferred is a carboxylate having 10 to 25 carbon atoms, more preferred is a carboxylate having 12 to 22 carbon atoms, and particularly preferred is a carboxylate having 14 to 20 carbon atoms. When the number of carbons is too large, generality tends to be lacking, and when the number of carbons is too small, purging performance tends to be insufficient due to insufficient surface activity during melting.
That is, the organic salt is preferably a Group 2 metal salt of a carboxylic acid having 14 to 20 carbon atoms, and most preferably a magnesium carboxylate having 14 to 20 carbon atoms.
かかる有機塩の融点は、通常100〜220℃、好ましくは110〜180℃、特に好ましくは120〜160℃である。有機塩が流路内で溶融した場合、界面活性能が発揮される点で好ましい。 The melting point of such an organic salt is usually 100 to 220 ° C, preferably 110 to 180 ° C, particularly preferably 120 to 160 ° C. When the organic salt is melted in the flow path, it is preferable in that the surface activity is exhibited.
上記無機塩とは無機化合物由来のアニオンを有する塩を意味し、例えば、ホウ酸塩、リン酸塩、炭酸塩、硫酸塩等が挙げられる。中でも、EVOH樹脂を分解する効果が高く洗浄効果が高い点から、塩基性の無機塩が好ましく、特に好ましくは、炭酸塩である。
なお、中でも炭酸マグネシウムは、塩基性炭酸マグネシウムの状態で安定であり、この状態で市販されているので、好ましい。The said inorganic salt means the salt which has an anion derived from an inorganic compound, For example, borate, a phosphate, carbonate, a sulfate, etc. are mentioned. Among these, basic inorganic salts are preferable and carbonates are particularly preferable from the viewpoint that the effect of decomposing the EVOH resin is high and the cleaning effect is high.
In particular, magnesium carbonate is preferable because it is stable in the state of basic magnesium carbonate and is commercially available in this state.
無機塩は樹脂流路内で溶融しないため、樹脂流路内にこびりついた被パージ樹脂を物理的にこそげ落とす効果を有すると考えられる。 Since the inorganic salt does not melt in the resin flow path, it is considered that the inorganic salt has an effect of physically scavenging the purged resin stuck in the resin flow path.
本発明のパージング剤を作製するために使用する金属塩の粒径は、成形性の観点や装置内での滞留を抑制するため小さい方がよい。好ましくは、レーザー回折散乱法による粒度分布測定において、金属塩の平均粒径は通常20ミクロン以下である。 The particle diameter of the metal salt used for producing the purging agent of the present invention is preferably small in order to suppress moldability and retention in the apparatus. Preferably, in the particle size distribution measurement by the laser diffraction scattering method, the average particle size of the metal salt is usually 20 microns or less.
本発明のパージング剤を作製するために使用する金属塩は、上記有機塩と無機塩を併用することが好ましい。特に、通常、重量比にて無機塩/有機塩=0.05〜10、好ましくは0.1〜8、特に好ましくは0.2〜5、殊に好ましくは1〜1.5である。
無機塩と有機塩の金属種は同一であっても異なるものであってもよい。パージング剤の排出性の点から、好ましくは同一種である。
そして、原料の経済性や生産性、洗浄効果の点から、無機塩として炭酸塩を用い、有機塩として長鎖脂肪族カルボン酸塩を用いることが好ましい。
最も好ましくは、無機塩として炭酸マグネシウムを用い、有機塩として炭素数14〜20のカルボン酸マグネシウム塩を用いるものである。The metal salt used to produce the purging agent of the present invention is preferably a combination of the organic salt and the inorganic salt. In particular, the weight ratio of inorganic salt / organic salt is generally 0.05 to 10, preferably 0.1 to 8, particularly preferably 0.2 to 5, and particularly preferably 1 to 1.5.
The metal species of the inorganic salt and the organic salt may be the same or different. From the point of discharge of the purging agent, the same species is preferred.
And it is preferable to use carbonate as an inorganic salt and long-chain aliphatic carboxylate as an organic salt from the point of economical efficiency and productivity of a raw material, and a cleaning effect.
Most preferably, magnesium carbonate is used as the inorganic salt, and magnesium carboxylate having 14 to 20 carbon atoms is used as the organic salt.
かかる金属塩において無機塩と有機塩を併用する場合、金属塩による被パージ樹脂分解による洗浄効果が高められる。さらに、無機塩は融点が通常500℃以上であり、一般的な熱可塑性樹脂の溶融成形温度よりもはるかに高いために樹脂流路内で溶融せず、樹脂流路壁に残存する被パージ樹脂を摩擦によってこそぎ落とす役割を担っていると考えられる。そして、高級脂肪酸塩等の有機塩は界面活性剤の一種であるため、樹脂流路内部に付着した被パージ樹脂を金属表面から浮かび上がらせて剥がす効果を有すると推測される。 In the case where an inorganic salt and an organic salt are used in combination in such a metal salt, the cleaning effect due to decomposition of the purged resin by the metal salt is enhanced. Furthermore, since the inorganic salt has a melting point of usually 500 ° C. or higher and is much higher than the melt molding temperature of a general thermoplastic resin, it does not melt in the resin flow path and remains on the resin flow path wall. It is thought that it plays a role of scrubbing off by friction. And since organic salts, such as a higher fatty acid salt, are 1 type of surfactant, it is estimated that it has the effect which the to-be-purged resin adhering to the inside of a resin flow path floats from a metal surface, and peels off.
[その他成分]
本発明のパージング剤には、必要に応じて、パージング剤全量に対して通常3重量%未満、好ましくは1重量%未満にて、ヒンダードフェノール、あるいはヒンダードアミン類等の熱安定剤、シリコン系またはフッ素系脂肪酸エステル、アミド系滑剤、発泡剤、フィラー(金属酸化物、水酸化物等)などを含有していてもよい。[Other ingredients]
In the purging agent of the present invention, the heat stabilizer such as hindered phenol or hindered amines, usually less than 3% by weight, preferably less than 1% by weight with respect to the total amount of the purging agent, silicon-based or Fluorine fatty acid ester, amide lubricant, foaming agent, filler (metal oxide, hydroxide, etc.) and the like may be contained.
[パージング剤のせん断粘度比]
本発明のパージング剤は、下記式より求められるせん断粘度比が特定範囲であることを最大の特徴とする。
せん断粘度比 = η(X)/η(Y)
[ここで、η(X)は温度230℃、せん断速度12.2sec−1のせん断粘度(Pa・S)、η(Y)は温度230℃、せん断速度1824sec−1のせん断粘度(Pa・S)である。][Shear viscosity ratio of purging agent]
The purging agent of the present invention is characterized in that the shear viscosity ratio obtained from the following formula is in a specific range.
Shear viscosity ratio = η (X) / η (Y)
[Here, eta (X) is a temperature 230 ° C., the shear viscosity of the shear rate 12.2sec -1 (Pa · S), η (Y) is a temperature 230 ° C., the shear viscosity of the shear rate 1824sec -1 (Pa · S ). ]
かかるせん断粘度比は、通常12.0〜16.0であり、好ましくは12.5〜15.0であり、特に好ましくは13.0〜14.5である。せん断粘度比が低すぎると、被パージ樹脂の洗浄、除去効果が十分に得られない傾向があり、一方で、高すぎると、パージング剤自身が排出されにくい傾向がある。なお、上記のパージング剤のせん断粘度比は、キャピラリーレオメーター(流動特性測定装置)を用いて230℃・各せん断速度のせん断粘度を測定し、その結果から算出することができる。 Such shear viscosity ratio is usually 12.0 to 16.0, preferably 12.5 to 15.0, particularly preferably 13.0 to 14.5. If the shear viscosity ratio is too low, the effect of cleaning and removing the resin to be purged tends to be insufficient, while if too high, the purging agent itself tends to be difficult to be discharged. The shear viscosity ratio of the purging agent can be calculated from the results obtained by measuring the shear viscosity at 230 ° C. and each shear rate using a capillary rheometer (flow characteristic measuring device).
温度230℃、せん断速度12.2sec−1の上記パージング剤のせん断粘度:η(X)は、通常1000〜4000Pa・Sであり、好ましくは1500〜3500Pa・Sであり、特に好ましくは2000〜3000Pa・Sである。Shear viscosity: η (X) of the purging agent at a temperature of 230 ° C. and a shear rate of 12.2 sec −1 is usually 1000 to 4000 Pa · S, preferably 1500 to 3500 Pa · S, and particularly preferably 2000 to 3000 Pa. -S.
温度230℃、せん断速度1824sec−1の上記パージング剤のせん断粘度:η(Y)は、通常60〜340Pa・Sであり、好ましくは100〜280Pa・Sであり、特に好ましくは130〜240Pa・Sである。The purging agent having a temperature of 230 ° C. and a shear rate of 1824 sec −1 has a shear viscosity: η (Y) of usually 60 to 340 Pa · S, preferably 100 to 280 Pa · S, particularly preferably 130 to 240 Pa · S. It is.
また、本発明のパージング剤のメルトフローレート(MFR)は、230℃、荷重2160gにて0.2〜20g/10分であることが好ましく、より好ましくは0.5〜15g/10分、特に好ましくは1〜10g/10分である。かかる値が大きすぎる場合、パージング効果が十分に発揮されない傾向がある。 The melt flow rate (MFR) of the purging agent of the present invention is preferably 0.2 to 20 g / 10 min at 230 ° C. and a load of 2160 g, more preferably 0.5 to 15 g / 10 min, and particularly Preferably it is 1-10 g / 10min. When this value is too large, the purging effect tends not to be sufficiently exhibited.
<パージング剤の製造方法>
本発明のパージング剤は、上記した金属塩と、ベースとなる炭化水素系樹脂とをコンパウンドして作製するものである。
かかるコンパウンドには公知の手法を用いることが可能である。なかでも、押出機を用いることが加工性、経済性の点で好ましい。押出機の種類は特に限定されず、単軸押出機、二軸押出機、多軸押出機等の一般的押出機が採用可能である。
押出機にてコンパウンドする際の押出機のバレル温度は通常150〜300℃、好ましくは160〜280℃、特に好ましくは170〜250℃である。<Method for producing purging agent>
The purging agent of the present invention is prepared by compounding the above-described metal salt and a base hydrocarbon resin.
A known method can be used for such a compound. Of these, the use of an extruder is preferable from the viewpoint of processability and economy. The type of the extruder is not particularly limited, and a general extruder such as a single-screw extruder, a twin-screw extruder, or a multi-screw extruder can be employed.
The barrel temperature of the extruder when compounding with the extruder is usually 150 to 300 ° C, preferably 160 to 280 ° C, particularly preferably 170 to 250 ° C.
そして、かかるパージング剤中の金属塩は、ベースとなる炭化水素系樹脂中に均一に分散していることが好ましい。 And it is preferable that the metal salt in this purging agent is disperse | distributing uniformly in the hydrocarbon resin used as a base.
本発明のパージング剤は上記のようにコンパウンドした後に、ペレットとすることが好ましい。ペレットとする方法は公知の方法が採用可能である。かかるペレットは、通常球形、円柱形、立方体形、直方体形等が上げられ、円柱形ペレットが好ましく、その直径は通常1〜5mm、長さは通常1〜5mmである。 The purging agent of the present invention is preferably formed into pellets after compounding as described above. A known method can be adopted as a method of forming pellets. Such pellets usually have a spherical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, etc., and a cylindrical pellet is preferable, and the diameter is usually 1 to 5 mm and the length is usually 1 to 5 mm.
<被パージ樹脂>
本発明のパージング剤の対象となる熱可塑性樹脂(すなわち被パージ樹脂)は、エチレン−ビニルエステル系共重合体ケン化物樹脂(EVOH樹脂)を含む。EVOH樹脂は、溶融成形機の金属に付着しやすく、かつ除去しにくい特性を有する高極性熱可塑性樹脂である。極性基含有熱可塑性樹脂は、そのガスバリア性能から食品等の包装材の中間層として使用されることが多く、中でもEVOH樹脂はガスバリア性に優れ、安全性も良好であるため、汎用されている。本発明のパージング剤は、このようなEVOH樹脂を含む被パージ樹脂のパージに効果的に用いることができる。<Purged resin>
The thermoplastic resin (that is, the purged resin) that is the object of the purging agent of the present invention includes an ethylene-vinyl ester copolymer saponified resin (EVOH resin). EVOH resin is a high-polarity thermoplastic resin that has a characteristic that it easily adheres to the metal of a melt molding machine and is difficult to remove. Polar group-containing thermoplastic resins are often used as an intermediate layer for packaging materials such as foods because of their gas barrier performance. Among them, EVOH resins are widely used because of their excellent gas barrier properties and good safety. The purging agent of the present invention can be effectively used for purging of the purged resin containing such EVOH resin.
[EVOH樹脂]
本発明で用いるEVOH樹脂は、通常、エチレンとビニルエステル系モノマーを共重合させた後にケン化させることにより得られる樹脂であり、非水溶性の熱可塑性樹脂である。重合法も公知の任意の重合法、例えば、溶液重合、懸濁重合、エマルジョン重合を用いることができるが、一般的にはメタノールを溶媒とする溶液重合が用いられる。得られたエチレン−ビニルエステル共重合体のケン化も公知の方法で行い得る。
すなわち、EVOH樹脂は、ビニルアルコール構造単位とビニルアルコール構造単位を主とし、ケン化されずに残存した若干量のビニルエステル構造単位を含むものである。[EVOH resin]
The EVOH resin used in the present invention is usually a resin obtained by copolymerization of ethylene and a vinyl ester monomer and then saponification, and is a water-insoluble thermoplastic resin. As the polymerization method, any known polymerization method such as solution polymerization, suspension polymerization, and emulsion polymerization can be used. In general, solution polymerization using methanol as a solvent is used. Saponification of the obtained ethylene-vinyl ester copolymer can also be performed by a known method.
That is, the EVOH resin mainly contains a vinyl alcohol structural unit and a vinyl alcohol structural unit, and contains a slight amount of vinyl ester structural unit remaining without being saponified.
上記ビニルエステル系モノマーとしては、市場入手性や製造時の不純物処理効率がよい点から、代表的には酢酸ビニルが用いられる。この他、例えばギ酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、バーサチック酸ビニル等の脂肪族ビニルエステル、安息香酸ビニル等の芳香族ビニルエステル等が挙げられ、通常炭素数3〜20、好ましくは炭素数4〜10、特に好ましくは炭素数4〜7の脂肪族ビニルエステルである。これらは通常単独で用いるが、必要に応じて複数種を同時に用いてもよい。 As the vinyl ester monomer, vinyl acetate is typically used from the viewpoint of market availability and good impurity treatment efficiency during production. In addition, for example, aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, benzoic acid, etc. Examples thereof include aromatic vinyl esters such as vinyl, and are usually aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. These are usually used alone, but a plurality of them may be used simultaneously as necessary.
EVOH樹脂におけるエチレン構造単位の含有量は、ISO14663に基づいて測定した値で、通常20〜60モル%、好ましくは25〜50モル%、特に好ましくは25〜35モル%である。かかる含有量が低すぎる場合は、高湿度条件下でのガスバリア性、溶融成形性が低下する傾向があり、逆に高すぎる場合は、ガスバリア性が不足する傾向がある。 The content of the ethylene structural unit in the EVOH resin is a value measured based on ISO 14663, and is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 35 mol%. If the content is too low, gas barrier properties and melt moldability under high humidity conditions tend to be reduced, and conversely if too high, gas barrier properties tend to be insufficient.
EVOH樹脂におけるビニルエステル成分のけん化度は、JIS K6726(ただし、EVOH樹脂は水/メタノール溶媒に均一に溶解した溶液にて)に基づいて測定した値で、通常90〜100モル%、好ましくは95〜100モル%、特に好ましくは99〜99.9モル%である。かかるケン化度が低すぎる場合にはガスバリア性、熱安定性、耐湿性等が低下する傾向がある。 The saponification degree of the vinyl ester component in the EVOH resin is a value measured based on JIS K6726 (however, the EVOH resin is a solution uniformly dissolved in water / methanol solvent), and is usually 90 to 100 mol%, preferably 95. -100 mol%, particularly preferably 99-99.9 mol%. When the degree of saponification is too low, gas barrier properties, thermal stability, moisture resistance and the like tend to decrease.
また、メルトインデクサー(押出式プラストメーター)を用いて測定した該EVOH樹脂のメルトフローレート(MFR)(210℃、荷重2,160g)は、通常0.5〜100g/10分であり、好ましくは1〜50g/10分、特に好ましくは3〜35g/10分である。かかるMFRが大きすぎる場合には、製膜性が不安定となる傾向があり、小さすぎる場合には粘度が高くなり過ぎて溶融押出しが困難となる傾向がある。 Further, the melt flow rate (MFR) (210 ° C., load 2,160 g) of the EVOH resin measured using a melt indexer (extrusion plastometer) is usually 0.5 to 100 g / 10 minutes, preferably Is 1 to 50 g / 10 min, particularly preferably 3 to 35 g / 10 min. When the MFR is too large, the film forming property tends to be unstable, and when it is too small, the viscosity becomes too high and melt extrusion tends to be difficult.
また、本発明におけるEVOH樹脂は、本発明の効果を阻害しない範囲(例えば10モル%以下)で、以下に示すコモノマーに由来する構造単位が、さらに含まれていてもよい。
前記コモノマーは、プロピレン、1−ブテン、イソブテン等のオレフィン類、3−ブテン−1−オール、3−ブテン−1,2−ジオール、4−ペンテン−1−オール、5−ヘキセン−1,2−ジオール等のヒドロキシ基含有α−オレフィン類やそのエステル化物、アシル化物などの誘導体、アクリル酸、メタクリル酸、クロトン酸、(無水)フタル酸、(無水)マレイン酸、(無水)イタコン酸等の不飽和酸類あるいはその塩あるいは炭素数1〜18のモノまたはジアルキルエステル類、アクリルアミド、炭素数1〜18のN−アルキルアクリルアミド、N,N−ジメチルアクリルアミド、2−アクリルアミドプロパンスルホン酸あるいはその塩、アクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のアクリルアミド類、メタアクリルアミド、炭素数1〜18のN−アルキルメタクリルアミド、N,N−ジメチルメタクリルアミド、2−メタクリルアミドプロパンスルホン酸あるいはその塩、メタクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のメタクリルアミド類、N−ビニルピロリドン、N−ビニルホルムアミド、N−ビニルアセトアミド等のN−ビニルアミド類、アクリルニトリル、メタクリルニトリル等のシアン化ビニル類、炭素数1〜18のアルキルビニルエーテル、ヒドロキシアルキルビニルエーテル、アルコキシアルキルビニルエーテル等のビニルエーテル類、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、臭化ビニル等のハロゲン化ビニル化合物類、トリメトキシビニルシラン等のビニルシラン類、酢酸アリル、塩化アリル等のハロゲン化アリル化合物類、アリルアルコール、ジメトキシアリルアルコール等のアリルアルコール類、トリメチル−(3−アクリルアミド−3−ジメチルプロピル)−アンモニウムクロリド、アクリルアミド−2−メチルプロパンスルホン酸等のコモノマー挙げられる。Further, the EVOH resin in the present invention may further contain structural units derived from the comonomer shown below within a range not inhibiting the effects of the present invention (for example, 10 mol% or less).
The comonomer includes olefins such as propylene, 1-butene and isobutene, 3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, 5-hexene-1,2- Hydroxyl group-containing α-olefins such as diols, derivatives thereof such as esterified products and acylated products, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, etc. Saturated acids or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkyl acrylamides having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or salts thereof, acrylamidopropyl Acrylic acid such as dimethylamine or its acid salt or its quaternary salt Methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide, 2-methacrylamideamidesulfonic acid or its salt, methacrylamidepropyldimethylamine or its acid salt or its quaternary Methacrylamides such as salts, N-vinyl amides such as N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxy Vinyl ethers such as alkyl vinyl ethers and alkoxyalkyl vinyl ethers, vinyl chlorides, vinylidene chloride, vinyl halides such as vinyl fluoride, vinylidene fluoride and vinyl bromide, vinyls such as trimethoxyvinyl silane Allyl halide compounds such as silane, allyl acetate, allyl chloride, allyl alcohol such as allyl alcohol, dimethoxyallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropane And comonomers such as sulfonic acid.
さらに、ウレタン化、アセタール化、シアノエチル化、オキシアルキレン化等の「後変性」されたEVOH系樹脂を用いることもできる。 Furthermore, “post-modified” EVOH-based resins such as urethanization, acetalization, cyanoethylation, oxyalkyleneation, and the like can also be used.
特に、ヒドロキシ基含有α−オレフィン類を共重合したEVOH樹脂は、二次成型性が良好になる点で好ましく、中でも1,2−ジオールを側鎖に有するEVOH樹脂が好ましい。
かかる1,2−ジオールを側鎖に有するEVOH樹脂は、側鎖に1,2−ジオール構造単位を含むものである。かかる1,2−ジオール構造単位とは、具体的には下記構造単位(1)で示される構造単位である。In particular, an EVOH resin obtained by copolymerizing a hydroxy group-containing α-olefin is preferable in terms of good secondary moldability, and among them, an EVOH resin having a 1,2-diol in the side chain is preferable.
Such EVOH resin having 1,2-diol in the side chain contains 1,2-diol structural units in the side chain. The 1,2-diol structural unit is specifically a structural unit represented by the following structural unit (1).
[一般式(1)において、R1、R2、及びR3はそれぞれ独立して水素原子または有機基を示し、Xは単結合または結合鎖を示し、R4、R5、及びR6はそれぞれ独立して水素原子または有機基を示す。][In General Formula (1), R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an organic group, X represents a single bond or a bonded chain, and R 4 , R 5 , and R 6 represent Each independently represents a hydrogen atom or an organic group. ]
上記一般式(1)で表される1,2−ジオール構造単位における有機基としては、特に限定されず、例えばメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、tert−ブチル基等の飽和炭化水素基、フェニル基、ベンジル基等の芳香族炭化水素基、ハロゲン原子、水酸基、アシルオキシ基、アルコキシカルボニル基、カルボキシル基、スルホン酸基等が挙げられる。
R1〜R3は通常炭素数1〜30、特には炭素数1〜15、さらには炭素数1〜4の飽和炭化水素基または水素原子が好ましく、水素原子が最も好ましい。R4〜R6は通常炭素数1〜30、特には炭素数1〜15、さらには炭素数1〜4のアルキル基または水素原子が好ましく、水素原子が最も好ましい。特に、R1〜R6がすべて水素であるものが最も好ましい。The organic group in the 1,2-diol structural unit represented by the general formula (1) is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. And saturated hydrocarbon groups such as tert-butyl group, aromatic hydrocarbon groups such as phenyl group and benzyl group, halogen atom, hydroxyl group, acyloxy group, alkoxycarbonyl group, carboxyl group and sulfonic acid group.
R 1 to R 3 are usually a saturated hydrocarbon group or a hydrogen atom having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably a hydrogen atom. R 4 to R 6 are preferably an alkyl group having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms, or a hydrogen atom, and most preferably a hydrogen atom. In particular, it is most preferable that R 1 to R 6 are all hydrogen.
また、一般式(1)で表わされる構造単位中のXは、代表的には単結合である。
なお、本発明の効果を阻害しない範囲であれば結合鎖であってもよい。かかる結合鎖としては特に限定されないが、アルキレン、アルケニレン、アルキニレン、フェニレン、ナフチレン等の炭化水素鎖(これらの炭化水素はフッ素原子、塩素原子、臭素原子等のハロゲン原子等で置換されていてもよい)の他、−O−、−(CH2O)m−、−(OCH2)m−、−(CH2O)mCH2−等のエーテル結合部位を含む構造、−CO−、−COCO−、−CO(CH2)mCO−、−CO(C6H4)CO−等のカルボニル基を含む構造、−S−、−CS−、−SO−、−SO2−等の硫黄原子を含む構造、−NR−、−CONR−、−NRCO−、−CSNR−、−NRCS−、−NRNR−等の窒素原子を含む構造、−HPO4−等のリン原子を含む構造などのヘテロ原子を含む構造、−Si(OR)2−、−OSi(OR)2−、−OSi(OR)2O−等の珪素原子を含む構造、−Ti(OR)2−、−OTi(OR)2−、−OTi(OR)2O−等のチタン原子を含む構造、−Al(OR)−、−OAl(OR)−、−OAl(OR)O−等のアルミニウム原子を含む構造などの金属原子を含む構造等が挙げられる。なお、Rは各々独立して任意の置換基であり、水素原子、アルキル基が好ましく、またmは自然数であり、通常1〜30、好ましくは1〜15、さらに好ましくは1〜10である。その中でも製造時あるいは使用時の安定性の点で−CH2OCH2−、および炭素数1〜10の炭化水素鎖が好ましく、さらには炭素数1〜6の炭化水素鎖、特には炭素数1であることが好ましい。Moreover, X in the structural unit represented by the general formula (1) is typically a single bond.
In addition, a bond chain may be used as long as the effect of the present invention is not inhibited. The bonding chain is not particularly limited, but is a hydrocarbon chain such as alkylene, alkenylene, alkynylene, phenylene, naphthylene or the like (these hydrocarbons may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom). ) other, -O -, - (CH 2 O) m -, - (OCH 2) m -, - (CH 2 O) m CH 2 - structure containing an ether binding site, such as, -CO -, - COCO -, - CO (CH 2) m CO -, - CO (C 6 H 4) CO- structure containing a carbonyl group such as, -S -, - CS -, - SO -, - SO 2 - , etc. sulfur atoms structure containing, -NR -, - CONR -, - NRCO -, - CSNR -, - NRCS -, - structure containing a nitrogen atom such as NRNR-, -HPO 4 - heteroatoms such structure containing a phosphorus atom, such as A structure containing- i (OR) 2 -, - OSi (OR) 2 -, - OSi (OR) structure containing 2 O- such as silicon atoms, -Ti (OR) 2 -, - OTi (OR) 2 -, - OTi ( OR) 2 O— and other structures including titanium atoms, —Al (OR) —, —OAl (OR) —, structures including aluminum atoms such as —OAl (OR) O—, and the like. Can be mentioned. In addition, R is an arbitrary substituent each independently, a hydrogen atom and an alkyl group are preferable, and m is a natural number, and is 1-30 normally, Preferably it is 1-15, More preferably, it is 1-10. Among them, —CH 2 OCH 2 — and a hydrocarbon chain having 1 to 10 carbon atoms are preferable from the viewpoint of stability at the time of production or use, and further, a hydrocarbon chain having 1 to 6 carbon atoms, particularly 1 carbon atom. It is preferable that
上記一般式(1)で表される1,2−ジオール構造単位における最も好ましい構造は、R1〜R6がすべて水素原子であり、Xが単結合であるものである。すなわち、下記構造式(1a)で示される構造単位が最も好ましい。The most preferable structure in the 1,2-diol structural unit represented by the general formula (1) is one in which R 1 to R 6 are all hydrogen atoms and X is a single bond. That is, the structural unit represented by the following structural formula (1a) is most preferable.
特に、上記一般式(1)で表わされる1,2−ジオール構造単位を含有する場合、その含有量は通常0.1〜20モル%、さらには0.1〜15モル%、特には0.1〜10モル%のものが好ましい。 In particular, when the 1,2-diol structural unit represented by the general formula (1) is contained, the content thereof is usually 0.1 to 20 mol%, further 0.1 to 15 mol%, and particularly preferably 0.1. The thing of 1-10 mol% is preferable.
また、本発明で使用されるEVOH樹脂は、異なる他のEVOH樹脂との混合物であってもよく、かかる他のEVOH樹脂としては、一般式(1)で表わされる1,2−ジオール構造単位の含有量が異なるもの、エチレン含有量が異なるもの、ケン化度が異なるもの、重合度が異なるもの、MFRが異なるもの、他の共重合成分が異なるものなどを挙げることができる。 In addition, the EVOH resin used in the present invention may be a mixture with other different EVOH resins. Examples of such other EVOH resins include 1,2-diol structural units represented by the general formula (1). Examples include those having different contents, those having different ethylene contents, those having different saponification degrees, those having different polymerization degrees, those having different MFRs, and those having different other copolymerization components.
本発明で用いられるEVOH樹脂には、本発明の効果を阻害しない範囲において、一般にEVOH樹脂に配合する配合剤、例えば、熱安定剤、酸化防止剤、帯電防止剤、着色剤、紫外線吸収剤、滑剤、可塑剤、光安定剤、界面活性剤、抗菌剤、乾燥剤、アンチブロッキング剤、難燃剤、架橋剤、硬化剤、発泡剤、結晶核剤、防曇剤、生分解用添加剤、シランカップリング剤、酸素吸収剤などが含有されていてもよい。 In the EVOH resin used in the present invention, a compounding agent generally blended with the EVOH resin, for example, a heat stabilizer, an antioxidant, an antistatic agent, a colorant, an ultraviolet absorber, within a range not inhibiting the effects of the present invention. Lubricant, plasticizer, light stabilizer, surfactant, antibacterial agent, drying agent, antiblocking agent, flame retardant, crosslinking agent, curing agent, foaming agent, crystal nucleating agent, antifogging agent, biodegradation additive, silane A coupling agent, an oxygen absorbent, etc. may be contained.
上記熱安定剤としては、溶融成形時の熱安定性等の各種物性を向上させる目的で、酢酸、プロピオン酸、酪酸、ラウリル酸、ステアリン酸、オレイン酸、ベヘニン酸等の有機酸類またはこれらのアルカリ金属塩(ナトリウム、カリウム等)、アルカリ土類金属塩(カルシウム、マグネシウム等)、亜鉛塩などの塩;または、硫酸、亜硫酸、炭酸、リン酸、ホウ酸等の無機酸類、またはこれらのアルカリ金属塩(ナトリウム、カリウム等)、アルカリ土類金属塩(カルシウム、マグネシウム等)、亜鉛塩などの塩等の添加剤を予め少量添加してもよい。 The heat stabilizer is an organic acid such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid, or an alkali thereof for the purpose of improving various physical properties such as heat stability during melt molding. Metal salts (sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), salts such as zinc salts; or inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid, boric acid, or alkali metals thereof Additives such as salts such as salts (sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), zinc salts, etc. may be added in small amounts in advance.
被パージ樹脂中、EVOH樹脂の含有量は1重量%以上であることが好ましく、被パージ樹脂の1〜99重量%が許容される。なお、被パージ樹脂をEVOH樹脂のみから構成してもよい。 In the purged resin, the EVOH resin content is preferably 1% by weight or more, and 1 to 99% by weight of the purged resin is allowed. The purged resin may be composed of only EVOH resin.
極性基含有熱可塑性樹脂は水分によってガスバリア性が低下する傾向があるため、通常、表層として疎水性熱可塑性樹脂(例えばポリオレフィン系樹脂、ポリスチレン系樹脂、ポリエステル系樹脂等)および場合によって各層間に接着性樹脂(例えば、不飽和カルボン酸変性ポリオレフィン系樹脂等)を有する多層構造体として包装材等に使用される。 Since polar group-containing thermoplastic resins tend to lower gas barrier properties due to moisture, they are usually bonded as a surface layer with a hydrophobic thermoplastic resin (eg, polyolefin resin, polystyrene resin, polyester resin, etc.) and sometimes between each layer. Used as a packaging material or the like as a multilayer structure having a functional resin (for example, an unsaturated carboxylic acid-modified polyolefin resin).
上記多層構造体を製造する場合、その製造過程において生じるスクラップを回収し、該回収物を再度押出機にて溶融成形して新たな多層構造体の少なくとも1層としてリサイクルすることがしばしばある。
かかるリサイクル操作は、多層構造体を構成する極性基含有熱可塑性樹脂、疎水性熱可塑性樹脂や接着性樹脂を含む樹脂組成物を押出機にて溶融混合し、成形するものであるが、本発明のパージング剤は、このような極性の高い樹脂を含有する樹脂組成物を押出機からパージ、すなわち、洗浄して除去する為に用いる場合においても有効である。When manufacturing the multilayer structure, scraps generated in the manufacturing process are often recovered, and the recovered material is melt-molded again by an extruder and recycled as at least one layer of a new multilayer structure.
Such a recycling operation involves melting and mixing a resin composition containing a polar group-containing thermoplastic resin, a hydrophobic thermoplastic resin or an adhesive resin constituting the multilayer structure in an extruder, and the present invention. This purging agent is also effective when used for purging, that is, washing and removing, a resin composition containing such a highly polar resin from an extruder.
このように、本発明のパージング剤は、溶融成形機中のEVOH樹脂をパージに最適に用いることができるが、公知の熱可塑性樹脂に対しても同様に用いることができる。かかる熱可塑性樹脂は、融点(または非晶性樹脂の場合は流動開始温度)が通常100〜270℃、好ましくは120〜250℃、特に好ましくは150〜230℃の熱可塑性樹脂が挙げられる。このような熱可塑性樹脂としては、例えば、EVOH樹脂以外のビニルアルコール系樹脂(PVA樹脂等)、PA樹脂、ポリオレフィン系樹脂(直鎖状低密度ポリエチレン、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、エチレン−酢酸ビニル共重合体、アイオノマー、エチレン−プロピレン共重合体、エチレン−アクリル酸エステル共重合体、ポリプロピレン、プロピレン−α−オレフィン(炭素数4〜20のα−オレフィン)共重合体、ポリブテン、ポリペンテン等)、ポリオレフィン系樹脂に不飽和カルボン酸をグラフト変性した変性ポリオレフィン系樹脂、ポリエステル系樹脂、ポリ塩化ビニル系樹脂、熱可塑性ポリウレタン系樹脂、ポリ塩化ビニリデン、アクリル系樹脂、ポリスチレン系樹脂、ビニルエステル系樹脂、ポリエステルエラストマー、ポリウレタンエラストマー、塩素化ポリエチレン、塩素化ポリプロピレン、芳香族又は脂肪族ポリケトン等が挙げられ、これらは単独でも複数種を同時に用いてもよい。
なかでも、上記したように、高極性熱可塑性樹脂であるPVA樹脂等のビニルアルコール系樹脂、PA樹脂は、EVOH樹脂と同様に、効果的に洗浄できる。As described above, the purging agent of the present invention can be optimally used for purging the EVOH resin in the melt molding machine, but can also be used in the same manner for known thermoplastic resins. Examples of such thermoplastic resins include thermoplastic resins having a melting point (or a flow start temperature in the case of an amorphous resin) of usually 100 to 270 ° C, preferably 120 to 250 ° C, and particularly preferably 150 to 230 ° C. Examples of such thermoplastic resins include vinyl alcohol resins (PVA resins, etc.) other than EVOH resins, PA resins, polyolefin resins (linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene). , Ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene , Polypentene, etc.), modified polyolefin resins obtained by graft-modifying unsaturated carboxylic acids to polyolefin resins, polyester resins, polyvinyl chloride resins, thermoplastic polyurethane resins, polyvinylidene chloride, acrylic resins, polystyrene resins, Vinyl ester Examples thereof include resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, chlorinated polypropylene, aromatic or aliphatic polyketones, and these may be used alone or in combination.
In particular, as described above, vinyl alcohol resins such as PVA resin, which is a high-polarity thermoplastic resin, and PA resins can be effectively cleaned in the same manner as EVOH resins.
本発明のパージング剤は、金属塩を比較的多量に含有することで、EVOH樹脂、PVA樹脂等のビニルアルコール系樹脂に適用した場合、ビニルアルコール系樹脂ポリマー中に金属塩が移行し、該樹脂を分解する効果に優れるため、特に溶融成形機ダイ部等の狭く高温な箇所に付着したビニルアルコール系樹脂、特にEVOH樹脂を洗浄するのに効果的である。 The purging agent of the present invention contains a relatively large amount of metal salt, and when applied to a vinyl alcohol resin such as EVOH resin or PVA resin, the metal salt migrates into the vinyl alcohol resin polymer, and the resin In particular, it is effective for cleaning vinyl alcohol resin, particularly EVOH resin, adhering to a narrow and high temperature portion such as a melt molding machine die.
本発明の被パージ樹脂は公知一般の滑剤、金属酸化物(例えば顔料として用いられる酸化ケイ素、酸化チタン等)、酸化防止剤、乾燥剤、充填剤、酸素吸収剤を含有していてもよい。 The resin to be purged of the present invention may contain a known general lubricant, metal oxide (for example, silicon oxide, titanium oxide used as a pigment), antioxidant, desiccant, filler, oxygen absorber.
<対象となる溶融成形機>
上記被パージ樹脂の溶融成形時に用いられる溶融成形機としては特に限定されず一般的な押出機を用いることが可能である。例えば単軸押出機、二軸押出機、多軸押出機等が上げられるが、いずれでもよい。詳細には、単層キャスト押出機、単層インフレ押出機、単層ブロー押出機、射出成形機、多層キャスト押出機、多層インフレ押出機、多層ブロー押出機、共射出成形機なども使用される。<Target melt molding machine>
The melt molding machine used at the time of melt molding of the resin to be purged is not particularly limited, and a general extruder can be used. For example, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, etc. can be raised, but any of them may be used. In detail, single layer cast extruder, single layer inflation extruder, single layer blow extruder, injection molding machine, multilayer cast extruder, multilayer inflation extruder, multilayer blow extruder, co-injection molding machine etc. are also used .
<パージング方法>
本発明のパージング剤は、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩を比較的多量に含有することにより、被パージ樹脂中にパージング剤内の金属塩が移行し、かかる金属塩が被パージ樹脂を分解するため、流路が狭く高温の苛酷な環境である溶融成形機のダイ部分等においても優れたパージ性能となり、洗浄効果に優れるものである。<Purging method>
The purging agent of the present invention contains a relatively large amount of at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts, so that the metal salt in the purging agent is contained in the purged resin. Since this metal salt decomposes the resin to be purged, the purge performance is excellent even in the die portion of a melt molding machine having a narrow flow path and a severe environment with high temperature, and the cleaning effect is excellent.
さらに本発明のパージング剤を用いたパージング方法は、公知方法を採用可能である。具体的には、溶融成形機にて熱可塑性樹脂を溶融成形した後に、本発明のパージング剤を供給して溶融成形機内に充填し、次いで排出すればよい。 Furthermore, a publicly known method can be adopted as a purging method using the purging agent of the present invention. Specifically, after the thermoplastic resin is melt-molded by a melt molding machine, the purging agent of the present invention is supplied, filled in the melt molding machine, and then discharged.
上記熱可塑性樹脂(被パージ樹脂)の溶融成形時の溶融成形機の温度(例えば押出機においては押出機のバレル温度)は、通常150〜260℃である。 The temperature of the melt molding machine at the time of melt molding of the thermoplastic resin (resin to be purged) (for example, the barrel temperature of the extruder in the extruder) is usually 150 to 260 ° C.
かかる溶融成形機内部に本発明のパージング剤を充填する際の溶融成形機の温度(押出機においては押出機のバレル温度)は、通常180〜280℃であり、好ましくは200〜260℃、より好ましくは210〜260℃、特に好ましくは230〜260℃である。かかる温度が高過ぎる場合、パージング剤の粘度が低下し、被パージ樹脂の洗浄効果が低下する傾向があり、低過ぎる場合、パージング剤自身の排出性が低下する傾向がある。
ここで、熱可塑性樹脂の溶融成形時、またはパージング剤を充填する際の溶融成形機の温度は、例えば押出機においては、押出機のバレル温度、すなわち押出機のバレルの表面温度を意味する。押出機のバレルが複数のセクションを有しており、個々のセクションが異なる温度に設定されている場合は、そのうちの最高温度をバレル温度とする。The temperature of the melt molding machine (in the extruder, the barrel temperature of the extruder) when filling the inside of the melt molding machine with the purging agent of the present invention is usually 180 to 280 ° C, preferably 200 to 260 ° C. Preferably it is 210-260 degreeC, Most preferably, it is 230-260 degreeC. When the temperature is too high, the viscosity of the purging agent tends to decrease, and the cleaning effect of the purged resin tends to decrease. When the temperature is too low, the discharge performance of the purging agent itself tends to decrease.
Here, the temperature of the melt molding machine at the time of melt molding of the thermoplastic resin or filling with the purging agent means, for example, in the extruder, the barrel temperature of the extruder, that is, the surface temperature of the barrel of the extruder. When the barrel of the extruder has a plurality of sections and each section is set to a different temperature, the highest temperature is set as the barrel temperature.
本発明のパージング剤の使用量は、通常、溶融成形機の大きさおよび被パージ樹脂の汚れの程度で決定すればよいが、取り扱い性・経済性の点から通常溶融成形機の樹脂容量(バレル容積からスクリュー容積を除いた樹脂が充填され得る容積)の5〜100倍であり、好ましくは8〜50倍であり、特に好ましくは10〜30倍である。 The amount of the purging agent of the present invention is usually determined based on the size of the melt molding machine and the degree of contamination of the purged resin. 5 to 100 times, preferably 8 to 50 times, particularly preferably 10 to 30 times the volume that can be filled with the resin excluding the screw volume from the volume.
本発明のパージング方法において、パージング剤中の金属塩が被パージ樹脂内へ移行しやすいよう、パージング剤を押出機等の溶融成形機に供給して充填した後に、溶融成形機内部をパージング剤で満たした状態でスクリューを停止し、一定時間放置することが好ましい。かかる放置時間について、通常5分〜5時間であり、より好ましくは0.2〜3時間であり、特に好ましくは0.5〜2時間である。かかる時間が長過ぎる場合、生産性の低下あるいはパージング剤自体の劣化により洗浄効果が低下する傾向にあり、少なすぎる場合にはパージング効果が低下する傾向がある。
なお、パージング剤が押出機内に充満された後、スクリューを止めて一定時間放置し、その後、再びパージング剤を充填して一定時間放置するなど、パージング剤の溶融成形機内での滞留とさらなるパージング剤供給の工程を繰り返す場合、パージング剤の溶融成形機内での滞留時間の和が上記範囲内にあることが好ましい。In the purging method of the present invention, after the purging agent is supplied and filled in a melt molding machine such as an extruder so that the metal salt in the purging agent easily moves into the purged resin, the inside of the melt molding machine is filled with the purging agent. It is preferable to stop the screw in a full state and leave it for a certain period of time. The standing time is usually 5 minutes to 5 hours, more preferably 0.2 to 3 hours, and particularly preferably 0.5 to 2 hours. If the time is too long, the cleaning effect tends to decrease due to a decrease in productivity or the deterioration of the purging agent itself, and if too short, the purging effect tends to decrease.
After the purging agent is filled in the extruder, the screw is stopped and left for a certain period of time, and then the purging agent is filled again and left for a certain period of time. When repeating the supplying step, it is preferable that the sum of the residence times of the purging agent in the melt molding machine is within the above range.
また、押出機を用いる場合、パージング時の押出機のスクリュー回転数は、利便性の点から被パージ樹脂の成形時と同じでよい。実用性の点から通常5〜300rpmであり、好ましくは10〜250rpmであり、特に好ましくは10〜100rpmである。なお、パージング中にスクリュー回転数を周期的に上下させることにより、被パージ樹脂の押出効果が向上することが期待される。 Moreover, when using an extruder, the screw rotation speed of the extruder at the time of purging may be the same as that at the time of molding the resin to be purged from the viewpoint of convenience. From the point of practical use, it is usually 5 to 300 rpm, preferably 10 to 250 rpm, and particularly preferably 10 to 100 rpm. Note that it is expected that the extrusion effect of the purged resin is improved by periodically increasing and decreasing the screw rotation speed during purging.
以上のように本発明のパージング剤およびこれを用いたパージング方法は、パージング剤が比較的多量の金属塩を含有し、特定のせん断速度によるせん断粘度比が大きいため、流路が狭く高温の苛酷な環境である溶融成形機のダイ部分等においても優れた洗浄効果が得られるとの優れた効果が発揮されるものである。 As described above, the purging agent of the present invention and the purging method using the same contain a relatively large amount of metal salt and a large shear viscosity ratio due to a specific shear rate. The excellent effect that an excellent cleaning effect can be obtained even in a die portion of a melt molding machine, which is a difficult environment, is exhibited.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はその要旨を越えない限り、実施例の記載に限定されるものではない。
尚、例中「部」とあるのは、断りのない限り重量基準を意味する。EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the description of the examples unless it exceeds the gist.
In the examples, “part” means a weight basis unless otherwise specified.
<実施例1> <Example 1>
パージング剤として、直鎖状低密度ポリエチレン(株式会社NUC製“GS650“、MFR0.6g/10分(190℃、荷重2160g)、密度0.92g/cm3、温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)=2980、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)=201、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))=14.8)を90部用い、金属塩としてステアリン酸マグネシウム(堺化学工業株式会社製、SM−PG)5部および塩基性炭酸マグネシウム(協和化学工業株式会社製、軽質)5部を用い、これらをドライブレンドした。
尚、かかるパージング剤中の金属塩の含有量は、10重量%であり、炭化水素系樹脂に対する金属塩の含有量は、金属に換算して1.5重量%であり、パージング剤の温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)は2360、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)は175であり、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))は13.5であった。なお、せん断粘度比は、東洋精機株式会社製キャピラリーレオメーター「キャピログラフ1D」により、230℃・各せん断速度のせん断粘度を測定し、その結果から算出した。
かかるドライブレンド物を、二軸押出機を用いて以下の条件で溶融混練してペレット化した。
スクリュー径:30mmφ
押出機温度:C2/C3/C4/C5/C6・・・・・C16/D=80/120/180/210/220・・・・・220/230℃
吐出量:25kg/h
回転数:250rpm
得られたペレットのMFRは、230℃、荷重2160g条件下で1.3g/10分であった。As a purging agent, linear low density polyethylene (“GS650” manufactured by NUC Corporation, MFR 0.6 g / 10 min (190 ° C., load 2160 g), density 0.92 g / cm 3 , temperature 230 ° C., shear rate 12.2 sec. −1 shear viscosity (Pa · S) = 2980, temperature 230 ° C./shear rate 1824 sec −1 shear viscosity (Pa · S) = 201, shear viscosity ratio (temperature 230 ° C./shear rate 12.2 sec −1 shear 90 parts of viscosity (Pa · S) / temperature 230 ° C., shear rate (Pa · S) of shear rate 1824 sec −1 ) = 14.8), and magnesium stearate (manufactured by Sakai Chemical Industry Co., Ltd., SM) -PG) and 5 parts of basic magnesium carbonate (manufactured by Kyowa Chemical Industry Co., Ltd., light) were dry blended.
In addition, the content of the metal salt in the purging agent is 10% by weight, the content of the metal salt with respect to the hydrocarbon resin is 1.5% by weight in terms of metal, and the temperature of the purging agent is 230%. shear viscosity ° C. · shear rate 12.2sec -1 (Pa · S) is 2360, a shear viscosity (Pa · S) 175 of the temperature 230 ° C. · shear rate 1824Sec -1, shear viscosity ratio (temperature 230 ° C. · shear shear viscosity speed 12.2sec -1 (Pa · S) / shear viscosity of temperature 230 ° C. · shear rate 1824sec -1 (Pa · S)) was 13.5. The shear viscosity ratio was calculated from the results obtained by measuring the shear viscosity at 230 ° C. and each shear rate with a capillary rheometer “Capillograph 1D” manufactured by Toyo Seiki Co., Ltd.
The dry blend was melt kneaded and pelletized using a twin screw extruder under the following conditions.
Screw diameter: 30mmφ
Extruder temperature: C2 / C3 / C4 / C5 / C6 ... C16 / D = 80/120/180/210/220 ... 220/230 ° C
Discharge rate: 25kg / h
Rotation speed: 250rpm
The MFR of the obtained pellet was 1.3 g / 10 min under the conditions of 230 ° C. and a load of 2160 g.
<被パージ樹脂の熱劣化状態再現モデル実験>
下記の単軸押出機を用い、押出機およびダイ温度を下記のように設定し、エチレン−酢酸ビニル系共重合体ケン化物(エチレン含有量29モル%、ケン化度99.8モル%、MFR3.4g/10分(210℃、荷重2160g))を30分間供給しながら排出し、加熱したまま2時間放置してEVOH樹脂成形物の長時間製造後の状態を再現した。
スクリュータイプ:フルフライト
スクリュー径:40mmφ
L/D:28
スクリュー圧縮比:2.5
ダイ:コートハンガーダイ
押出機温度:C1/C2/C3/C4/H/D=220/250/260/260/260/240℃
回転数:40rpm<Experiment model for reproducing the heat degradation state of purged resin>
Using the following single-screw extruder, the extruder and die temperature were set as follows, and an ethylene-vinyl acetate copolymer saponified product (ethylene content 29 mol%, saponification degree 99.8 mol%, MFR 3 4 g / 10 min (210 ° C., load 2160 g)) was discharged while being supplied for 30 minutes, and the product was allowed to stand for 2 hours while being heated to reproduce the state after long-term production of the EVOH resin molded product.
Screw type: Full flight Screw diameter: 40mmφ
L / D: 28
Screw compression ratio: 2.5
Die: Coat hanger die Extruder temperature: C1 / C2 / C3 / C4 / H / D = 220/250/260/260/260/240 ° C.
Rotation speed: 40rpm
<パージング操作>
その後、上記の押出機温度のまま、上記パージング剤を20分間供給した。このとき、最初の10分間はスクリュー回転数を20rpmにし、次の10分間は40rpmとした。その後、上記の押出機温度にて、上記パージング剤を押出機内に充填したまま、1時間放置した。<Purging operation>
Thereafter, the purging agent was supplied for 20 minutes while maintaining the extruder temperature. At this time, the screw speed was 20 rpm for the first 10 minutes and 40 rpm for the next 10 minutes. Then, the above-described purging agent was filled in the extruder at the above-mentioned extruder temperature and left for 1 hour.
〔パージング効果〕
その後、EVOH樹脂を再び押出機に供給し、製膜を開始した。製膜を2時間行った後、押出機内のパージング剤を少量のポリエチレンで置換してから押出機を解体し、ダイの汚れ状況を観察し、下記評価基準により評価した。
◎:ダイには被パージ樹脂の付着物は全くなかった。
○:ダイに薄膜状でわずかに付着物が存在するが、付着物の粘度が十分低下しており、清掃が容易である。
△:ダイにやや厚めの樹脂層が付着しており、○の状態よりも清掃に時間を要する。
×:ダイに厚い樹脂層が付着しており、かつ付着物の粘度があまり低下していないので、△の状態よりも清掃に時間を要する。[Purging effect]
Then, EVOH resin was again supplied to the extruder, and film formation was started. After film formation was performed for 2 hours, the purging agent in the extruder was replaced with a small amount of polyethylene, and then the extruder was disassembled. The state of dirt on the die was observed and evaluated according to the following evaluation criteria.
A: There was no deposit of the resin to be purged on the die.
○: A thin film is present on the die and a slight amount of deposits are present, but the viscosity of the deposits is sufficiently reduced and cleaning is easy.
Δ: A slightly thicker resin layer is attached to the die, and it takes more time to clean than the state of ○.
X: A thick resin layer is adhered to the die, and the viscosity of the deposit is not lowered so much, so that it takes more time for cleaning than the state of Δ.
<実施例2>
実施例1において、炭化水素系樹脂として、直鎖状低密度ポリエチレン(株式会社NUC製“NUCG7641“、MFR0.6g/10分(190℃、荷重2160g)、密度0.922g/cm3、温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)=2710、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)=192、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))=14.1)を用いた以外は、実施例1と同様にパージング剤を作製し、同様に評価した。
なお、パージング剤の温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)は2390、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)は171であり、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))は14.0であった。<Example 2>
In Example 1, as a hydrocarbon-based resin, linear low density polyethylene (“NUCG7641” manufactured by NUC Corporation, MFR 0.6 g / 10 min (190 ° C., load 2160 g), density 0.922 g / cm 3 , temperature 230 ° C. · shear viscosity shear rate of 12.2sec -1 (Pa · S) = 2710, shear viscosity (Pa · S) of the temperature 230 ° C. · shear rate 1824sec -1 = 192, the shear viscosity ratio (temperature 230 ° C. · shear rate Purging as in Example 1 , except that 12.2 sec −1 shear viscosity (Pa · S) / temperature 230 ° C., shear rate 1824 sec −1 shear viscosity (Pa · S)) = 14.1) was used. Agents were prepared and evaluated in the same manner.
Incidentally, the shear viscosity of the temperature 230 ° C. · shear rate 12.2Sec -1 purging agent (Pa · S) is 2390, the shear viscosity of the temperature 230 ° C. · shear rate 1824sec -1 (Pa · S) is 171, shear viscosity ratio (shear viscosity shear viscosity temperature 230 ° C. · shear rate 12.2sec -1 (Pa · S) / temperature 230 ° C. · shear rate 1824sec -1 (Pa · S)) was 14.0.
<比較例1>
実施例1において、炭化水素系樹脂として、直鎖状低密度ポリエチレン(日本ポリエチレン株式会社製“ノバテックLLUF230“、MFR1.0g/10分(190℃、荷重2160g)、密度0.921g/cm3、温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)=3490、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)=274、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))=12.8)を用いた以外は、実施例1と同様にパージング剤を作製し、同様に評価した。
なお、パージング剤の温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)は2620、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)は238であり、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))は11.0であった。<Comparative Example 1>
In Example 1, as a hydrocarbon-based resin, linear low density polyethylene (“Novatech LLUF230” manufactured by Nippon Polyethylene Co., Ltd., MFR 1.0 g / 10 min (190 ° C., load 2160 g), density 0.921 g / cm 3 , shear viscosity of the temperature 230 ° C. · shear rate 12.2sec -1 (Pa · S) = 3490, shear viscosity (Pa · S) = 274 temperature 230 ° C. · shear rate 1824sec -1, shear viscosity ratio (temperature 230 ° C. · Example 1 except that the shear viscosity (Pa · S) at a shear rate of 12.2 sec −1 / temperature 230 ° C., the shear viscosity at a shear rate of 1824 sec −1 (Pa · S)) = 12.8) was used. A purging agent was prepared and evaluated in the same manner.
Incidentally, the shear viscosity of the temperature 230 ° C. · shear rate 12.2Sec -1 purging agent (Pa · S) is 2620, the shear viscosity of the temperature 230 ° C. · shear rate 1824sec -1 (Pa · S) is 238, shear The viscosity ratio (shear viscosity at a temperature of 230 ° C. and shear rate of 12.2 sec −1 (Pa · S) / shear viscosity at a temperature of 230 ° C. and shear rate of 1824 sec −1 (Pa · S)) was 11.0.
<比較例2>
実施例1において、炭化水素系樹脂として、メタロセン直鎖状低密度ポリエチレン(株式会社プライムポリマー製“SP1510“、MFR1.0g/10分(190℃、荷重2160g)、密度0.913g/cm3、温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)=3470、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)=312、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))=11.1)を用いた以外は、実施例1と同様にパージング剤を作製し、同様に評価した。
なお、パージング剤の温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)は2840、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)は261であり、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))は10.9であった。<Comparative example 2>
In Example 1, as a hydrocarbon resin, metallocene linear low density polyethylene (“Prime Polymer Co., Ltd.“ SP1510 ”, MFR 1.0 g / 10 min (190 ° C., load 2160 g), density 0.913 g / cm 3 , shear viscosity of the temperature 230 ° C. · shear rate 12.2sec -1 (Pa · S) = 3470, shear viscosity (Pa · S) = 312 temperature 230 ° C. · shear rate 1824sec -1, shear viscosity ratio (temperature 230 ° C. · except using shear viscosity (Pa · S) / shear viscosity of temperature 230 ° C. · shear rate 1824Sec -1 of shear rate 12.2Sec -1 a (Pa · S)) = 11.1 ), as in example 1 A purging agent was prepared and evaluated in the same manner.
Incidentally, the shear viscosity of the temperature 230 ° C. · shear rate 12.2Sec -1 purging agent (Pa · S) is 2840, the shear viscosity of the temperature 230 ° C. · shear rate 1824sec -1 (Pa · S) is 261, shear viscosity ratio (shear viscosity shear viscosity temperature 230 ° C. · shear rate 12.2sec -1 (Pa · S) / temperature 230 ° C. · shear rate 1824sec -1 (Pa · S)) was 10.9.
<比較例3>
実施例1において、炭化水素系樹脂として、メタロセン直鎖状低密度ポリエチレン(株式会社プライムポリマー製“SP2510“、MFR1.5g/10分(190℃、荷重2160g)、密度0.923g/cm3、温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)=2250、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)=264、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))=8.5)を用いた以外は、実施例1と同様にパージング剤を作製し、同様に評価した。
なお、パージング剤の温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)は2480、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)は220であり、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))は11.3であった。<Comparative Example 3>
In Example 1, as a hydrocarbon resin, metallocene linear low density polyethylene (“Prime Polymer Co., Ltd.“ SP2510 ”, MFR 1.5 g / 10 min (190 ° C., load 2160 g), density 0.923 g / cm 3 , shear viscosity (Pa · S) = 2250, the shear viscosity of the temperature 230 ° C. · shear rate 1824sec -1 (Pa · S) = 264 temperature 230 ° C. · shear rate 12.2sec -1, shear viscosity ratio (temperature 230 ° C. · Example 1 except that the shear viscosity (Pa · S) at a shear rate of 12.2 sec −1 / temperature 230 ° C., the shear viscosity at a shear rate of 1824 sec −1 (Pa · S)) = 8.5) was used. A purging agent was prepared and evaluated in the same manner.
In addition, the shear viscosity (Pa · S) of the purging agent at a temperature of 230 ° C. and a shear rate of 12.2 sec −1 is 2480, and the shear viscosity (Pa · S) at a temperature of 230 ° C. and a shear rate of 1824 sec −1 is 220. viscosity ratio (shear viscosity shear viscosity temperature 230 ° C. · shear rate 12.2sec -1 (Pa · S) / temperature 230 ° C. · shear rate 1824sec -1 (Pa · S)) was 11.3.
<比較例4>
実施例1において、炭化水素系樹脂として、メタロセン系直鎖状低密度ポリエチレン(住友化学株式会社製“スミカセンE FV104“、MFR1.0g/10分(190℃、荷重2160g)、密度0.913g/cm3、温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)=3920、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)=332、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))=11.8)を用いた以外は、実施例1と同様にパージング剤を作製し、同様に評価した。
なお、パージング剤の温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)は3310、温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S)は283であり、せん断粘度比(温度230℃・せん断速度12.2sec−1のせん断粘度(Pa・S)/温度230℃・せん断速度1824sec−1のせん断粘度(Pa・S))は11.7であった。<Comparative example 4>
In Example 1, as a hydrocarbon-based resin, a metallocene linear low-density polyethylene (“Sumikasen E FV104” manufactured by Sumitomo Chemical Co., Ltd., MFR 1.0 g / 10 min (190 ° C., load 2160 g), density 0.913 g / cm 3 , temperature 230 ° C./shear rate 12.2 sec −1 shear viscosity (Pa · S) = 3920, temperature 230 ° C./shear rate 1824 sec −1 shear viscosity (Pa · S) = 332, shear viscosity ratio (temperature except for using the shear viscosity of 230 ° C. · shear rate 12.2sec -1 (Pa · S) / shear viscosity of temperature 230 ° C. · shear rate 1824sec -1 (Pa · S)) = 11.8), example A purging agent was prepared in the same manner as in No. 1 and evaluated in the same manner.
Incidentally, the shear viscosity of the temperature 230 ° C. · shear rate 12.2Sec -1 purging agent (Pa · S) 3310, the shear viscosity of the temperature 230 ° C. · shear rate 1824sec -1 (Pa · S) is 283, shear The viscosity ratio (shear viscosity at a temperature of 230 ° C. and shear rate of 12.2 sec −1 (Pa · S) / shear viscosity at a temperature of 230 ° C. and shear rate of 1824 sec −1 (Pa · S)) was 11.7.
<参考例1>
実施例1で作製したパージング剤を用い、被パージ樹脂として直鎖状低密度ポリエチレン(株式会社NUC製“GS650“)を用いて、同様にパージング効果を評価した。<Reference Example 1>
The purging effect was similarly evaluated using the purging agent produced in Example 1 and using linear low density polyethylene (“GS650” manufactured by NUC Co., Ltd.) as the purged resin.
<参考例2>
比較例3で作製したパージング剤を用い、被パージ樹脂として直鎖状低密度ポリエチレン(株式会社プライムポリマー製“SP2510“)を用いて、同様にパージング効果を評価した。<Reference Example 2>
Using the purging agent prepared in Comparative Example 3 and using a linear low density polyethylene (“SP2510” manufactured by Prime Polymer Co., Ltd.) as the purged resin, the purging effect was similarly evaluated.
実施例1,2、比較例1〜4および参考例1,2の結果を表1に示す。 Table 1 shows the results of Examples 1 and 2, Comparative Examples 1 to 4, and Reference Examples 1 and 2.
表1からわかるように、特定のせん断速度のせん断粘度比が大きいパージング剤を用いた実施例1,2は、比較例1〜4に比べてパージング効果が良好であることが分かった。
また、実施例1、比較例3および参考例1,2からわかるように、比較例3で作製したパージング剤はポリエチレン樹脂に対してパージング効果を奏したにもかかわらず(参考例2)、EVOH樹脂に対しては効果が得られなかったのに対し、本発明のパージング剤はEVOH樹脂に対して効果的にパージング効果を得ることができることがわかった。As can be seen from Table 1, it was found that Examples 1 and 2 using a purging agent having a large shear viscosity ratio at a specific shear rate had better purging effects than Comparative Examples 1 to 4.
Further, as can be seen from Example 1, Comparative Example 3 and Reference Examples 1 and 2, the purging agent produced in Comparative Example 3 exhibited a purging effect on polyethylene resin (Reference Example 2), but EVOH. It was found that the purging agent of the present invention can effectively obtain the purging effect for the EVOH resin, whereas the effect was not obtained for the resin.
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、2013年11月26日出願の日本特許出願(特願2013−243495)及び2014年11月12日出願の日本特許出願(特願2014−229819)に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on November 26, 2013 (Japanese Patent Application No. 2013-243495) and a Japanese patent application filed on November 12, 2014 (Japanese Patent Application No. 2014-229819). Incorporated herein by reference.
本発明の特定のせん断粘度比を有するパージング剤は、パージング効果が良好であり、特に包装材として汎用されるEVOH樹脂に対するパージング効果に優れることから、工業的に極めて有用である。 The purging agent having a specific shear viscosity ratio of the present invention is very useful industrially because it has a good purging effect and particularly an excellent purging effect for EVOH resins widely used as packaging materials.
Claims (4)
炭化水素系樹脂と、アルカリ金属塩およびアルカリ土類金属塩からなる群より選ばれる少なくとも1種の金属塩とを含み、該炭化水素系樹脂に対する該金属塩の含有量が金属に換算して1重量%を超えて20重量%以下であり、下記式より求められるせん断粘度比が12〜16であるパージング剤。
せん断粘度比 = η(X)/η(Y)
[ここで、η(X)は温度230℃、せん断速度12.2sec−1のせん断粘度(Pa・S)であり、η(Y)は温度230℃、せん断速度1824sec−1のせん断粘度(Pa・S)である。]A purging agent used for purging a purged resin containing an ethylene-vinyl ester copolymer saponified resin,
A hydrocarbon resin and at least one metal salt selected from the group consisting of an alkali metal salt and an alkaline earth metal salt, and the content of the metal salt relative to the hydrocarbon resin is 1 in terms of metal. A purging agent that exceeds 20% by weight and is 20% by weight or less, and the shear viscosity ratio determined by the following formula is 12-16.
Shear viscosity ratio = η (X) / η (Y)
[Here, eta (X) is a temperature 230 ° C., a shear viscosity of the shear rate 12.2sec -1 (Pa · S), η (Y) is a temperature 230 ° C., the shear viscosity of the shear rate 1824sec -1 (Pa -S). ]
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JPH05279518A (en) * | 1992-03-31 | 1993-10-26 | Kuraray Co Ltd | Purging agent |
JPH1016024A (en) * | 1996-06-26 | 1998-01-20 | Nippon Synthetic Chem Ind Co Ltd:The | Purging agent |
JPH1067040A (en) * | 1996-06-18 | 1998-03-10 | Kuraray Co Ltd | Purging agent and purging method |
JP2006335913A (en) * | 2005-06-03 | 2006-12-14 | Daicel Polymer Ltd | Resin composition for cleaning |
JP2012031404A (en) * | 2010-07-08 | 2012-02-16 | Nippon Synthetic Chem Ind Co Ltd:The | Purging agent and purging method using the same |
JP2012171284A (en) * | 2011-02-23 | 2012-09-10 | Mitsubishi Gas Chemical Co Inc | Purging method |
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US5958313A (en) * | 1996-04-11 | 1999-09-28 | Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha | Purging agent |
EP0813948B1 (en) * | 1996-06-18 | 2003-10-08 | Kuraray Co., Ltd. | Purging agent and purging method |
WO2002047883A1 (en) * | 2000-12-13 | 2002-06-20 | Asahi Kasei Kabushiki Kaisha | Detergent |
CN100336892C (en) * | 2005-10-25 | 2007-09-12 | 杨新中 | Plastic screw cleaning agent and its compounding process and usage |
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Patent Citations (7)
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JPH05269754A (en) * | 1992-03-25 | 1993-10-19 | Kuraray Co Ltd | Purging agent |
JPH05279518A (en) * | 1992-03-31 | 1993-10-26 | Kuraray Co Ltd | Purging agent |
JPH1067040A (en) * | 1996-06-18 | 1998-03-10 | Kuraray Co Ltd | Purging agent and purging method |
JPH1016024A (en) * | 1996-06-26 | 1998-01-20 | Nippon Synthetic Chem Ind Co Ltd:The | Purging agent |
JP2006335913A (en) * | 2005-06-03 | 2006-12-14 | Daicel Polymer Ltd | Resin composition for cleaning |
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JP2012171284A (en) * | 2011-02-23 | 2012-09-10 | Mitsubishi Gas Chemical Co Inc | Purging method |
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